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| United States Patent |
5,346,943
|
|
Khungar
, et al.
|
September 13, 1994
|
Sealer composition for wood, concrete, porous materials
Abstract
A water-based wax-free stable emulsion composition, useful as water sealer
for wood, concrete and porous materials is disclosed. The water-based
sealer composition forms a non-drying film that is water-repellant,
flexible, self-sealing and allows passage of water vapor. The water-based
sealer composition contains less than 400 grams per liter of volatile
organic compounds. The water-based sealer composition is especially suited
for above-grade applications in that it protects against absorption of
water.
| Inventors:
|
Khungar; Sohan L. (Woodridge, IL);
Graves, Jr.; L. Martin (Bolingbrook, IL);
Gryziecki; Robin M. (Aurora, IL)
|
| Assignee:
|
Amoco Corporation (Chicago, IL)
|
| Appl. No.:
|
027957 |
| Filed:
|
March 8, 1993 |
| Current U.S. Class: |
524/398; 106/285; 524/399; 524/579; 524/773; 524/801; 524/804 |
| Intern'l Class: |
C08L 023/20; C08K 005/01; C08K 005/09; C08K 005/17 |
| Field of Search: |
524/398,399,579,773,801,804
106/285
|
References Cited
U.S. Patent Documents
| 2402331 | Jun., 1946 | Kvalnes | 524/773.
|
| 3036977 | May., 1962 | Koch et al. | 524/315.
|
| 4176109 | Nov., 1979 | Kaiya et al. | 524/315.
|
| 4983454 | Jan., 1991 | Hiraki et al. | 428/416.
|
| 5049186 | Sep., 1991 | Kawabata | 524/277.
|
| 5169884 | Dec., 1992 | Lindemann et al. | 524/45.
|
Primary Examiner: Michl; Paul R.
Assistant Examiner: Merriam; Andrew E. C.
Attorney, Agent or Firm: Kanady; Mary Jo, Oliver; Wallace L.
Claims
That which is claimed is:
1. A C.sub.4 linear polymer water-based wax-free stable emulsion
composition used as a sealer for wood, concrete, porous materials first
prepared as a stable gel wherein said gel has a viscosity of less than
about 5000 centipoise at room temperature from a non-hydrogenated liquid
homopolymer selected from the group consisting of polybutene and
polyisobutylene with a number average molecular weight of from about 300
to about 10,000, a gel-forming metal soap of a carboxylic acid of from
about 12 to about 20 carbon atoms, an amine to reduce the viscosity of
said gel selected from the group consisting of triethylamine,
triethanolamine and morpholine, a hydrocarbon solvent, an emulsifier which
is optionally a nonionic emulsifier, a cationic emulsifier, an anionic
emulsifier and mixtures thereof, and an emulsifying-stablizing agent
consisting of an acrylic acid copolymer crosslinked with a polyalkenyl
polyether wherein said liquid homopolymer is present in an amount of less
than 10 wt. percent, said metal soap is present in an amount of from about
1 wt % to 5 wt %, said amine in an amount of from about 0.1 wt. % to 2.0
wt. %, said emulsifier in an amount of from about 0.5 wt. % to about 5 wt.
%, said emulsifying-stabilizing agent is present in an amount of from
about 0.02 wt. % to about 2.0 wt. %, and said hydrocarbon solvent is
present in an amount less than about 35 weight percent of the emulsion
composition, wherein said amounts are in percentages of the weight of the
water emulsion wherein pH of said emulsion composition is within the range
of from about 7 to about 10.
2. The polymer emulsion composition of claim 1 wherein said hydrocarbon
solvent is selected from the group consisting of turpentine, mineral
spirits and mixtures thereof.
3. The polymer emulsion composition of claim 1 wherein said metal soap is
formed by metals selected from the group consisting of aluminum, calcium,
cobalt, lead and zinc.
4. The polymer emulsion composition of claim 1 wherein said gel is prepared
in the presence of an emulsifier selected from the group consisting of a
sorbitan fatty acid ester, isostearic acid, oleic acid, lauric acid, tall
oil fatty acids, tallow fatty acids, hydrogenated tallow fatty acids, and
mixtures thereof.
5. The polymer emulsion composition of claim 1 wherein said metal soap is
an aluminum distearate comprising about 95% distearate and about 5%
monostearate.
6. The polymer emulsion composition of claim 1 wherein said emulsifier is a
cationic emulsifier and is selected from the group consisting of
triethylamine, triethylanolamine, morpholine and mixtures thereof.
7. The polymer emulsion composition of claim 1 which contains a fluorinated
surfactant for water repellancy.
8. The polymer emulsion composition of claim 1 wherein said emulsifier is
an anionic emulsifier and is selected from the group consisting of
isostearic acid and oleic acid, said anionic emulsifier being present in
an amount of from about 1 wt. % to about 5 wt. % of the weight of the
final emulsion.
9. The polymer emulsion composition of claim 1 wherein said homopolymer is
a polybutene of number average molecular weight of from about 300 to about
3000, said metal soap is an aluminum stearate, said amine is selected from
the group consisting of triethylamine and triethanolamine, said
hydrocarbon solvent is selected from the group consisting of mineral
spirits and turpentine, and said stable emulsion is prepared in the
presence of an emulsifier and an emulsifying-stabilizing agent.
10. The polymer emulsion composition of claim 9 wherein said emulsifier is
a sorbitan fatty acid ester.
11. The polymer emulsion composition of claim 9 wherein said
emulsifying-stabilizing agent is an acrylic acid copolymer crosslinked
with a polyalkenyl polyether.
12. The polymer emulsion composition of claim 9 wherein said
emulsifying-stabilizing agent is a low molecular weight diester of a
linear alcohol of from 6 to 12 carbon atoms and a mono-, di- and
tricarboxylic acid of 6 to 12 carbon atoms.
Description
BACKGROUND OF THE INVENTION
This invention relates to a novel sealer composition and to a method for
its preparation. This invention also relates to a sealer composition
containing less than 400 grams/liter volatile organic compounds (VOC).
More particularly, it relates to an aqueous composition for the protection
of wood, concrete, masonry and other porous materials to minimize the
amount of water absorbed by the wood or other material to which it is
applied. The invented composition can also be used as a parting agent, or
bond breaker, or as a release agent for forms in concrete construction and
as a protective coating to prevent corrosion of metal manufactures exposed
to the elements of rain and/or snow in above-grade applications. The
composition protects against the absorption of water and is particularly
suited for sealer applications wherein reduced environmental pollution
emissions are required.
DESCRIPTION OF THE PRIOR ART
A number of waterproofing and sealing compounds have been developed for
wood, masonry, concrete and other porous materials. For example,
water-based acrylic polymer wood sealers are known in the art. Acrylic
polymer latex-based sealers exhibit desirable qualities such as good
flexibility, good adhesion to many substrates and resistance to
ultraviolet radiation. However, these acrylic polymer latex sealers suffer
from one or more serious weaknesses, namely poor wet adhesion and poor
barrier properties against water penetration. Attempts have been made to
improve the water barrier properties of these latex sealers. For example,
see U.S. Pat. No. 4,897,291 wherein a sealer composition for a wood
product is disclosed which comprises an aqueous vehicle, a water-based
emulsion of a styrene-butadiene copolymer, a carboxylated styrene-acrylic
copolymer, a paraffin wax, and a water-soluble methyl siliconate. U.S.
Pat. No. 4,340,524 teaches addition of a hydrophobic resin in a
non-gelling organic solvent into an acrylic latex to improve its water
resistance after a short cure period.
An example of a masonry sealing compound is taught in U.S. Pat. No.
3,546,007 wherein a thin coating of a composition comprising a mineral
lubricating oil, a soap thickener and an oil-soluble polymer selected from
the group consisting of atactic polypropylene, atactic propylene-ethylene
copolymer and ethylene vinyl acetate copolymer. The composition is applied
to prevent seepage and ground water from penetrating through masonry
foundations.
These examples illustrate the wide utility of sealer compositions. A sealer
composition can be waterproof in that it creates a condition which is
impervious to water and water vapor, whether or not the water is under
pressure, or a sealer composition can create a condition of water
repellency wherein the sealer composition repels water without
significantly reducing the permeability of the structure to the passage of
water vapor.
Heretofore, hydrocarbon wax has found extensive application in
water-proofing or otherwise protecting various materials. Hydrocarbon wax
has been used because it remains solid at room temperature, has a definite
melting point at relatively low temperatures and is hydrophobic.
Hydrocarbon wax is usually impregnated in or coated on fibrous material
such as wood, fabric, as well as articles of cement and the like. To
effect impregnation or coating of the hydrocarbon wax, the wax is usually
heated to melt, dissolved in a solvent, or emulsified in water. It has
been found to be best applied as an emulsion, considering safety, economy
and workability.
Although hydrocarbon wax is hydrophobic, its emulsion when coated and dried
at room temperature does not create a water-proof surface. It is believed
that the surface coated by the dried emulsion consists of a distribution
of discrete wax particles with interstices which permit passage of water
therethrough.
Liquid polybutadiene, polybutene, or a polyisobutylene have been combined
with hydrocarbon wax to prepare a protective film which is substantially
transparent, highly cohesive, water-resistant and water-proof. U.S. Pat.
No. 4,468,254 teaches a wax composition comprising (1) 100 parts by weight
of a hydrocarbon wax having a melting point of 40.degree.-120.degree. C.
and (2) 3-25 parts by weight of a polymer of the group consisting of a
liquid polybutadiene having a number average molecular weight of
500-10,000, a polybutene having a number average molecular weight of
300-3,000, and a polyisobutylene having viscosity average molecular weight
of 20,000-50,000, the compositions being emulsified in water.
U.S. Pat. No. 4,594,109 discloses an aqueous composition for the protection
of paint surfaces which comprises (a) a solid emulsion component composed
of (1) an oxygen-containing wax, (2) a polybutene and (3) a silicone oil;
(b) a powdery emulsion component composed of (4) substantially
white-colored fine powder of a silicon-containing inorganic-material and
(5) white-colored fine powder of a silicon-free inorganic or organic
material and (c) an emulsifier component. However, water-based wax-powder
dispersions are accompanied by drawbacks in that the barrier coats are
susceptible to separation, as is noted in U.S. Pat. No. 5,049,186.
Water-based wax emulsions, although they do not suffer from pollution or
safety problems due to the absence of a hydrocarbon solvent, suffer from
the problems of dryability upon application to a surface and
dispersability. In addition, such wax emulsion compositions are required
to have mutually-contradictory properties; they are required to be
emulsifiable in aqueous compositions but water repellent when applied to a
surface and exposed to rain and moisture. U.S. Pat. No. 5,049,186 teaches
a disperse phase composition containing a petroleum wax in conjunction
with an oxygen-containing wax, an ethylene/.alpha.-olefin copolymer and a
fatty acid metal salt, and an emulsifier component overcomes the
aforementioned problems. In an example, calcium stearate as the fatty acid
metal salt and morpholine as an emulsifier were used. A comparative
composition containing polybutene instead of an ethylene/.alpha.-olefin
copolymer gave a poor barrier coat test. The barrier coat test required
exposure of coated plates to sunlight in summer for three months. Some
changes were observed in the polybutene-wax barrier coat as compared with
the ethylene/.alpha.-olefin copolymer coat.
U.K. Patent Application GB 2,018,261A teaches a composition for sealing or
caulking joints, especially of foundry or metallurgical equipment. The
composition comprises a binder and inorganic filler material. The binder
comprises a non-drying oil, a gelling agent, and a liquid polymer of
molecular weight of from 2,000 to 10,000. Suitable gelling agents include
aluminum soaps of stearic acid such as aluminum stearate. A preferred
liquid polymer is polybutene of 2,000 molecular weight. The binder
composition is prepared by mixing with heating. The resulting sealer
composition containing inorganic filler of up to 80%, when extruded into
strings, demonstrates minimal adhesiveness, presumably because of the
large percentage of inorganic filler present, despite the inclusion of
polybutene which is typically sticky.
Polybutenes are non-drying unsaturated hydrocarbons which are hydrophobic
in nature. Therefore formulation of polybutenes in a sealer compound could
improve water-resistance. It is also known that aluminum stearates react
with hydrocarbons to form gels, such as taught in U.K. Patent Application
GB 2,018,261A, wherein a polybutene composition is gelled in the presence
of a non-drying oil, such as a mineral oil.
Metal soaps, such as aluminum stearate are well-known to effect the
gelation of oils and polar organic solvents when heated with these liquids
or formed in situ. Upon cooling, the resulting solutions set to a gel
(Kirk-Othmer, 3rd Ed., Vol. 8, p. 45). These gels have been used in
greases, lubricants, thickeners and taught as solvent-based sealers.
Aluminum stearate is well-known as a moisture repellant in cosmetics.
Aqueous emulsions containing polybutenes have been taught in the prior art.
U.S. Pat. No. 4,594,109 teaches an aqueous polybutene composition but the
aqueous emulsion comprises predominantly hydrocarbons other than
polybutenes, specifically 100 parts by weight of an oxygen-containing wax
to 0.1-60 parts by weight of a polybutene. Oxygen-containing waxes having
an oxygen content not less than 3.0% by weight are taught as being
satisfactorily emulsified with the aid of a small amount of emulsifier.
Examples teach a maximum ratio of wax to polybutene of 4:1. U.S. Pat. No.
4,468,254 teaches a wax emulsion comprising a hydrocarbon wax admixed with
a liquid polymer selected from the group consisting of polybutadiene,
polybutene and polyisobutylene, 100 parts by weight of hydrocarbon wax to
3-25 parts by weight of the liquid polymer.
However, despite the numerous attempts to modify sealer compositions
containing hydrocarbon wax with other components, the problems inherent in
a wax composition remain to some degree. Wax crystals can be fragile and
rupture through use, thus creating fissures and breaks in the coating.
Also, although wax is hydrophobic, it is considered that a surface coated
by a dried wax emulsion consists of a distribution of discrete wax
particles with interstices which permit passage of water. A wax coating is
also subject to abrasion from use which can impair the wax sealer
properties.
It is an object of this invention to provide a water-based sealer
composition which is wax-free, which upon application forms a non-drying
film that is a water-repellant coating with good flexibility and permits
swelling of a substrate without cracking of the coating. It is further an
object of this invention to provide a coating which is self-sealing to
cracks in the surface coating and yet allows passage of water vapor. It is
further an object of this invention to provide a sealer composition
containing less than 400 grams/liter volatile organic compound (VOC) and
which reduces the possibilities of environmental pollution and fire
hazard.
SUMMARY OF THE INVENTION
This invention relates to a water-based, wax-free stable emulsion
composition useful as a sealer for wood, concrete and porous materials.
The sealer composition comprises polybutene, a heavy metal soap, an amine
in a minimal amount of solvent as a gel which in the presence of an
emulsifying-stabilizing agent forms a stable water emulsion for
application to a substrate. The emulsifying-stabilizing agent comprises an
acrylic acid polymer cross-linked with a polyalkenyl polyether or a
diester of a linear alcohol of from 6 to 12 carbon atoms and adipic acid.
The water-based sealer composition forms a non-drying film that is
water-repellant, flexible, self-sealing and allows passage of water vapor.
The water-based emulsion contains less than 400 grams/liter volatile
organic compounds.
DETAILED DESCRIPTION OF THE INVENTION
This invention comprises a water-based wax-free sealer for wood, concrete
and other porous materials for above-grade applications which contains a
minimum of organic solvent and reduces the hazards of environmental
pollution and fire. The water-based composition is a water emulsion of an
organic solvent-based composition which is prepared from a linear polymer
of butene and a heavy metal.
The C.sub.4 linear polymer of butene is a non-hydrogenated liquid
homopolymer with a number average molecular weight range of from about 300
to about 10,000. These polymers are available as polybutenes from
polymerization of refinery butenes, e.g., isobutylene, cis-butene-2, and
butene-1 generally present with butane in a C.sub.4 fraction. Commercially
available since about 1940, such C.sub.4 fractions with or without added
isobutylene or isobutylene-rich concentrates typically have been
polymerized in the presence of Friedel-Crafts catalysts, such as aluminum
halides, feric halides, zinc halides, boron halides (i.e., BF.sub.3), tin
halides, mercuric halides, and titanium halides.
The wide range in viscosity and molecular weight depends, as is known, on
polymerization temperature, catalyst and its concentration, and on the
olefin content of the feed.
The resultant viscous polybutenes are permanently liquid, possess tack and
stickiness and have found use as components of caulking compounds,
adhesives, electric cable insulating oils, as a raw material for
manufacture for motor oil additives and as a component of wax compositions
to improve waterproofness of wax films. A characteristic which has limited
application of polybutenes in films and coatings has been the sticky film
or coating which results if the percentage of polybutene in the
formulation is greater than about 25%. The viscous polybutenes are
employed in the composition of the present invention in an amount to about
10% by weight, or less, of the weight of the water emulsion.
The heavy metal soap or thickening agent, preferably an aluminum soap,
employed in the sealer of the present invention is used in an amount
ranging from about 1 to about 5%, and more particularly from about 1 to
about 3% based upon weight of the final composition. The aluminum soap is
most often a soap of a saturated or unsaturated higher aliphatic
carboxylic acid containing from about 12 to 20 carbon atoms; e.g.,
stearic, oleic, ricinoleic or palmitic acid and mixtures thereof. Mixed
aluminum soaps, which are soaps obtained from a higher carboxylic acid and
from a carboxylic acid with a lower molecular weight may be used. Examples
of such aluminum soaps include soaps of benzostearic, acetopalmitic,
toluostearic, etc. An aluminum stearic acid soap is preferred. More
preferably, an aluminum distearic acid soap with no more than about 5%
aluminum monostearic acid soap present is preferred.
The process of preparing the sealer composition comprises first the
preparation of a gel of the polybutene component and the aluminum stearate
soap to which is added an amine and an organic hydrocarbon solvent which
can be mineral spirits or turpentine. The resulting gel comprising a fatty
acid and an amine or an alkanolamine, is converted into a stable water
emulsion with the aid of an emulsifying-stabilizing agent selected from
the group consisting of an acrylic acid polymer crosslinked with a
polyalkenyl polyether or a low molecular weight ester of adipic acid. The
presence of the amine serves to reduce the viscosity of the gel to less
than about 5000 centipoise at room temperature, measured by a Brookfield
viscometer, spindle No. 2 at 0.5 rpm. The amine is present in an amount of
from about 0.01 wt. % to about 2.0 wt. %.
It is essential for uniform application of the sealer composition that a
stable emulsion be prepared despite the hydrophobic characteristics of a
C.sub.4 olefinic linear polymer of butene and a metal soap. Otherwise the
emulsion will separate and/or break into its components, thus handicapping
the mechanical application of the sealer composition to a substrate and
the film forming properties of the sealer composition. It has been found
that a stable gel of a C.sub.4 olefinic linear polymer of butene and a
metal soap can be emulsified to form a stable emulsion with addition of a
emulsifying-stabilizing agent of from about 0.02 to about 0.05 weight % of
the weight of the water-based emulsion wherein the emulsifying-stabilizing
agent is an acrylic acid polymer crosslinked with a polyalkenyl polyether
or a low molecular weight polyester. A suitable emulsifying-stabilizing
agent is one of a Carbopol.RTM. 1600-series copolymer, B. F. Goodrich
Company, Specialty Polymers & Chemical Division, Calvert City, Ky., or a
diester of a C.sub.6 to C.sub.12 linear alcohol and adipic acid, Werner G.
Smith, Inc., Cleveland, Ohio.
To test the effectiveness of various emulsifier agents, a typical
formulation comprising polybutene, aluminum stearate, triethylamine and a
solvent, either mineral spirits or turpentine, was prepared as a gel. The
gel composition was emulsified in water in the presence of an emulsifying
agent. The prepared water emulsions of a polybutene and aluminum stearate
either separated in periods of as short as 10 minutes to several hours or
the emulsion broke. A stable emulsion resulted only with addition of an
acrylic acid copolymer crosslinked with a polyalkenyl polyether, a
Carbopol.RTM. copolymer, or a C.sub.6 to C.sub.12 linear alcohol diester,
Smithol 50.
Requirements for successful application of Carbopol.RTM. copolymers require
a polar medium such as water, a pH of 4 or 5 or higher, the presence of a
low level of soluble salts, and a temperature which does not exceed
85.degree. C.
The acrylic acid copolymer crosslinked with a polyalkenyl polyether acts as
a primary emulsifier and as an emulsion stabilizer. An amine preferably is
present as a nonionic surfactant to provide a pH within the range of about
7 to 10. The emulsified composition does not include a high level of
soluble salts although an amine salt is present.
The constituents of the composition of the invention will now be described
in further detail:
A suitable C.sub.4 olefinic linear polymer of butene is one of a group of
liquid polybutadiene, polybutene, and polyisobutylene. The liquid C.sub.4
olefinic linear polymer of butene has a number average molecular weight of
300-10,000, preferably 800-5,000. Polymers of lower number average
molecular weight than 300 would result in a weak and less water resistant
coating film when applied to a substrate, and greater than 10,000 would
cause difficulty in emulsifying the composition in water and would be
tacky. Specific examples of the liquid polybutadiene are not only low
homopolymers of butadiene, but also include copolymers of butadiene and
one or more of conjugated diolefins of 4-5 carbon atoms such as isoprene
and piperylene, and low molecular weight copolymers of butadiene, with or
without said conjugated diolefins, and aliphatic or aromatic vinyl
monomers having an ethylene unsaturation such as isobutylene,
diisobutylene, styrene, .alpha.-methyl styrene, vinyl toluene, and divinyl
benzene. These butadiene polymers may be obtained by any conventional
method. For example, an anionic polymerization method may be employed in
which butadiene alone or with conjugated diolefins of 4-5 carbon atoms is
polymerized with styrene, .alpha.-methyl styrene, vinyl toluene or divinyl
benzene in an amount of less than 50 mol % based on butadiene in the
presence of an alkali metal or an alkali organo-metal catalyst at
0.degree.-100.degree. C. In such instance, a chain transfer polymerization
method is applicable in which an organometal compound such as benzyl
sodium is used as catalyst and toluene or other compounds having alkylaryl
groups is used as a chain transfer agent so as to obtain a light color
polymer which has a controlled molecular weight and minimum gel as
disclosed in U.S. Pat. No. 3,789,090.
Polybutene, which can be a component useful in the invention, has a number
average molecular weight of 300-3,000, preferably 450-1,500. Polybutene
departing from this range below 300 would be a liquid of low viscosity,
resulting in a very weak film. Polybutene of greater than 3,000 in this
molecular weight would be too viscous and tacky, and hence difficult to be
emulsified in water.
The polybutene useful in this invented composition has its source from
mixtures of butene-1, butene-2, isobutylene and butanes which may be
processed by any suitable known methods. A typical example of such known
method comprises reacting a starting material of butane-butene fraction
(available as side-product during the cracking of naphtha into ethylene or
propylene) at -30.degree. to +30.degree. C. in the presence of a
Friedel-Crafts catalyst such as aluminum chloride, magnesium chloride,
boron fluoride, titanium tetrachloride and complexes thereof, or with or
without addition of an organic halide or chloric acid, in which instance
no solvent is required as butane and unreacted olefins act as the solvent.
The resulting polybutene is usually settled in a tank to remove the
catalyst and is, if necessary, washed with alkali, water, nitric acid,
sulfuric acid, oxalic acid and the like, or further treated with an
aluminum oxide and activated clay to complete removal of all residual
catalyst particles. The treated product may be washed to separate
unreacted gas, stripped of light polymers and further, if necessary,
refined. In the present invention, it is possible to use a hydrogenated
polybutene obtained by hydrogenating the double bonds of the polybutene by
methods already known in the art, such as by using nickel as a catalyst.
Polyisobutylene, another component which may be useful in the invented
composition has a viscosity average molecular weight of 20,000-50,000,
preferably 20,000-40,000. It is a highly viscous, low-fluidity,
semi-liquid material. Polyisobutylenes of a viscosity average molecular
weight exceeding 50,000 are a semi-rubber which is hard to dissolve or
emulsify in the usual manner so therefore are less preferred. The
polyisobutylene which may be used in the invention is prepared by the
polymerization of isobutylenes available from a butane-butene fraction or
from dehydration of tertiary butylalcohol or diacetone alcohol which may
be refined by molecular sieve. The isobutylene feed is polymerized at
-80.degree. to 150.degree. C., as is well known, with the addition of
ethylene or propane as diluent and boron trifluoride or aluminum chloride.
The emulsifier useful in the solvent colloid preparation is a suitable
cationic emulsifier which includes amines such as triethylamine,
triethanolamine, morpholine and the like.
In the water-emulsion preparation, the surfactant may be chosen from a wide
variety of usual surface active agents. Nonionic, cationic and anionic
emulsifiers are all usable. Suitable nonionic emulsifiers include sorbitan
esters (Span.RTM.20, Span.RTM.40, Span.RTM.60, Span.RTM.80, Tween.RTM.60,
Tween.RTM.80) and mixtures thereof. (ICI Americas, Inc., Wilmington, Del.)
When a cationic emulsifier is used, its effect can be enhanced by adding
an anionic emulsifier, e.g., isostearic acid, oleic acid, lauric acid,
tall oil fatty acids, tallow fatty acids, hydrogenated tallow fatty acids,
in an amount less than the equivalent amount of the cationic emulsifier.
As noted above, it is essential for the preparation of a stable emulsion
that the emulsion contain a suitable emulsifying-stabilizing agent
selected from the group consisting of an acrylic acid copolymer
crosslinked with a polyalkenyl polyether or a low molecular weight ester
selected from the group consisting of an ester of a C.sub.6 to C.sub.12
linear alcohol and a mono-, di- and tricarboxylic acid of 6 to 12 carbon
atoms.
The solvent in the gel preparation can be mineral spirits or turpentine.
The mineral spirits are of petroleum origin not less 10% of which distill
below 175.degree. C. and which not less than 95% distill below 240.degree.
C. The turpentine is preferably steam distilled from gum turpentine.
Mineral spirits and steam distilled turpentine are commercially available.
Gel formation requires the presence of a heavy metal soap formed by metals
heavier than sodium, e.g., aluminum, calcium, cobalt, lead and zinc, and a
fatty acid of from 12 to about 20 carbon atoms. A preferred heavy metal
soap is an aluminum distearate commercially available as about 95%
distearate and about 5% monostearate.
A fluorinated surfactant can be added to the formulation to decrease water
absorption. A suitable surfactant is Fluorad.RTM. FC-430, or Fluorad.RTM.
FC-129, Minnesota Mining and Manufacturing Company, (3M), St. Paul,
Minneapolis, Minn.
In summary, this invention relates to a water-based wax-free emulsion
composition useful as a sealer for wood, concrete and porous materials
which comprises a C.sub.4 linear polymer of butene with a number average
molecular weight of from about 300 to about 10,000, a metallic soap
selected from the group consisting of a soap formed from a metal selected
from the group consisting of aluminum, calcium, cobalt, lead and zinc, an
amine and an organic hydrocarbon solvent present in an amount less than
35% by weight of the emulsion composition wherein a composition of said
C.sub.4 linear polymer of butene, metallic soap, amine and organic
hydrocarbon solvent is first prepared as a colloidal gel which is then
emulsified in water in the presence of an emulsifying agent selected from
the group consisting of cationic, anionic and nonionic surface agents
preferably selected from isostearic acid, and sorbitan monolaurates, and
in the further presence of a emulsifier-stabilizer agent selected from the
group consisting of an acrylic acid polymer crosslinked with a polyalkenyl
polyether and a low molecular weight diester of a C.sub.6 to C.sub.12
linear alcohol and a carboxylic acid of from 6 to 12 carbon atoms.
The following examples are exemplary only and are not to be construed as
limiting the scope of the invention.
EXAMPLE I
The precursor gel was prepared in the following manner. Polybutene,
aluminum stearate (technical), triethylamine, and turpentine (steam
distilled) were added in the following procedure to a one-half gallon
stainless steel beaker fitted with an electric heating mantle and equipped
with a stirrer.
______________________________________
Gel Parts %
Component By Weight Grams Weight
______________________________________
Polybutene.sup.1
1.000 200.00 18.05
Al Stearate.sup.2
0.183 36.60 3.30
Triethylamine.sup.3
0.085 17.00 1.53
Turpentine.sup.4
4.272 854.40 77.11
5.540 1108.00 99.99
______________________________________
Note:
.sup.1 H300 polybutene, number average molecular weight 1340, Amoco
Chemical Company, Chicago, IL.
.sup.2 Aluminum stearate, technical, BDH Chemicals, Ltd., Poole, DorsetBH
12 4NN, Great Britain
.sup.3 Triethylamine, Baker Analyzed Reagent, J. T. Baker Chemical Co.,
Philadelphia, PA.
.sup.4 Turpentine, steam distilled, technical grade, added to 22.89%
solids content.
The formulation was heated to 127.degree. C. (260.degree. F.) to about
182.degree. C. (350.degree. F.) to mix the formulation. The mixing
temperature initially was measured by means of a thermocouple placed next
to the wall of the beaker, between the wall of the beaker and the heating
mantle. After mixing for about one hour at about 3000 rpm with a Cowles
Series 2000 mixer, the thermocouple was inserted into the mixture and the
temperature was raised to at least 160.degree. C. (320.degree. F.) within
the range of from about 160.degree. C. (320.degree. F.) to about
182.degree. C. (360.degree. F.) wherein limited gelling of the formulation
occurred. Additional gelling occurred but the mixture still remained fluid
despite the application of heat. With the addition of turpentine, 427.20
grams, 50% of total final amount, the mixture thickened but addition of
the remaining turpentine, 427.20 grams, and triethylamine, 17 grams,
caused the mixture to become less thick and more fluid. The mixture was
then filtered through a paint strainer, mesh size 44.times.36, into a
one-half gallon stainless steel beaker. A quantity of the material which
did not flow readily remained upon the walls of the mixing vessel as a
gel. The gelled product was viscous and clear.
EXAMPLE II
A second batch of the precursor gel was prepared in the procedure of
Example I but gelling temperature was increased to 170.degree.-180.degree.
C. (330.degree.-356.degree. F.). The formulation gelled as a thin gel
within 45 minutes and gelled more firmly with addition of turpentine,
427.2 grams. Addition of the remaining turpentine, 427.20 grams and
triethylamine, 17 grams, diluted the thinned mixture to a gel-like
consistency. The material was then filtered through a paint strainer, mesh
size 44.times.36, where the gelled material clogged the paint strainer.
The gelled product was viscous and clear.
EXAMPLE III
In the procedure of Example II, a gel was prepared with an increased amount
of aluminum stearate which was increased to 40 wt. % of the polybutene.
The triethylamine was increased in proportion to the aluminum stearate.
The turpentine was decreased to give 34.6 wt. % solids.
______________________________________
Gel Parts %
Component By Weight Grams Weight
______________________________________
Polybutene H-300
1.000 240.00 21.82
Al Stearate 0.400 96.00 8.73
Triethylamine
0.186 44.64 4.06
Turpentine 2.998 719.52 65.40
4.584 1100.16 100.01
______________________________________
All components were the same as indicated in Example I.
The gelling process occurred within about 25 minutes at a temperature
within the range of from 170.degree.-180.degree. C.
(330.degree.-356.degree. F.). The gelled product was more viscous and less
clear than the gelled product of Examples I and II. Addition of
turpentine, 359.76 grams appeared to reduce the viscosity but the mixture
was not a clear material. The addition of triethylamine, 44.64 grams, did
not cause the mixture to become less viscous. Addition of more turpentine,
359.76 grams, also failed to reduce the viscosity but with additional
mixing, the mixture did become clear. The final product could not be
filtered because of its high viscosity and the presence of unreacted
triethylamine was evidenced by odor.
EXAMPLE IV
In the procedure of Example I, an emulsion base was prepared. An
emulsifying agent and water were then added. The formulation was as
follows:
______________________________________
Gel Parts %
Component By Weight Grams Weight
______________________________________
Polybutene H-300.sup.1
1.000 27.08 7.311
Al Stearate.sup.2
0.183 4.95 1.336
Triethylamine.sup.3
0.085 2.30 0.621
Turpentine.sup.4
4.272 115.67 31.230
Gel Total 5.540 150.00 40.498
Emulsion Component
Witconol .TM. 2650.sup.5
0.100 2.71 0.732
D.I. Water.sup.6
8.038 217.67 58.769
Total 13.678 370.38 99.999
______________________________________
Note:
.sup.1 Polybutene H300, Amoco Chemical Company, Chicago, IL.
.sup.2 Aluminum stearate, technical grade, BDH Chemicals, Ltd., Poole,
Dorset BH 12 4NN, Great Britain
.sup.3 Triethylamine, Baker Analytical Reagent, J. T. Baker Chemical Co.,
Philadelphia, PA.
.sup.4 Turpentine, steam distilled, technical grade
.sup.5 Emulsifier agent, Witco Corporation, Chicago, IL.
.sup.6 Deionized water
In the emulsification procedure, 150 grams of the emulsion base gel were
added to a 1.2 liter stainless steel beaker. The beaker was suspended in a
water bath. The emulsifying agent, Witconol 2650, was added to the
emulsion base heated to 80.degree.-90.degree. C. The beaker was taken out
of the bath and put under a Cowles mixer, Model 84. Water, at 90.degree.
C., was added slowly while mixing at 4000-5000 rpm over a period of about
8 minutes. Mixing at 4000-5000 rpm was continued for an additional 7
minutes for a total of 15 minutes mixing time.
Upon standing overnight at room temperature, the gel emulsion separated
into two phases.
To the previously separated emulsion, there was added, with mixing,
additional surfactant, Witconol 2650 in the following formulation:
______________________________________
Parts %
Component By Weight Grams Weight
______________________________________
Polybutene H-300
1.000 23.47 7.26
Aluminum Stearate
0.183 4.29 1.33
Triethylamine 0.085 1.99 0.62
Turpentine 4.272 100.26 31.01
Witconol 2650 0.200 4.70 1.46
D.I. Water 8.038 188.64 58.34
Total 13.778 323.35 100.02
______________________________________
The emulsion with the added surfactant did not separate upon standing
overnight. The emulsion showed a slight separation after 14 days at room
temperature.
EXAMPLE V
In the gel and emulsion formulation and procedure of Example IV,
commercially available emulsifying agents were tested for ability to
sustain at room temperature a gel emulsion of polybutene H-300 and
aluminum stearate in the presence of triethylamine and turpentine. The
results are in Table I.
TABLE I
______________________________________
Stability of Polybutene-Aluminum
Stearate Gel Emulsion With Emulsifying Agents
Emulsion Stability
Emulsifying Agent Separation into 2 Phases
______________________________________
Brij .RTM. 700 Within 90 minutes
Iconol TDA-10
Formula Amount Initial - within 60 minutes
Twice Formula Amount
24 hrs - two phases
Witconol 2650 24 hrs - two phases
Iconol TDA - 10 24 hrs - two phases
Sorbitan Monolaurate
Formula amount 8 hrs - two phases
Twice formula amount
17 days - two phases
Witconol/Emerest .RTM. 2640
Initial - within 10 minutes
Triton .RTM. X-45
Formula Amount Initial - within 60 minutes
Twice Formula Amount
14 days - two phases
PEG 600 Monolaurate, (Stepan)
Formula Amount Initial - 16 hours
Twice Formula Amount
48 hrs - two phases
Triton .RTM. X-100
Formula Amount Initial - 16 hours
Twice Formula Amount
Within 60 minutes
Oleic Acid 2 hrs - two phases
Isostearic Acid Within 10 minutes
Sorbitan Monolaurate (.75%) +
Within 15 minutes
Isostearic Acid (.25%)
Tween .RTM. 60 Within 60 minutes
Tween .RTM. 60 (50%) + Sorbitan
Within 10 minutes
Monolaurate (50%)
______________________________________
The above results indicate that many commercial emulsifying agents
available to practitioners of the art do not stabilize gel water-emulsions
of hydrophobic polybutene and hydrophobic aluminum stearate over an
extended period.
EXAMPLE VI
In a modified procedure of Example IV, an emulsion base Sample No.
15931-16, was prepared but using mineral spirits instead of turpentine. An
emulsifying agent comprising a mixture of isostearic acid and sorbitan
monolaurate was added. After the emulsion was formed with the emulsifying
agent to prepare Sample No. 15931-17, a stabilizing agent, a polyalkenyl
polyether, Carbopol.RTM. 1622, B. F. Goodrich company, Cleveland, Ohio was
added. Formulations and procedure were as follows:
______________________________________
Gel Parts %
Component By Weight Grams Weight
______________________________________
Polybutene H-300.sup.1
1.000 54.15 6.81
Al Stearate.sup.2
0.183 9.91 1.25
Triethanolamine.sup.3
0.085 4.6 0.58
Mineral Spirits.sup.4
4.272 231.34 29.10
Gel Total 5.540 300.00 37.74
Emulsion Component
Isostearic Acid.sup.5
0.150 8.12 1.02
Sorbitan Monolaurate.sup.6
0.050 2.71 0.34
Distilled Water
8.940 484.12 60.90
Total 14.680 794.95 100.00
______________________________________
Note:
.sup.1 Amoco Chemical Company, Chicago, IL.
.sup.2 No. 5503, Mallinckrodt Specialty Chemicals Company, St. Louis, MO.
.sup.3 Triethanolamine, TEXACO Chemical Co., Austin, TX.
.sup.4 Mineral Spirits, SHELL Corporation, Houston, TX.
.sup.5 Isostearic acid, Unichema Company, Chicago, IL.
.sup.6 Sorbitan monolaurate, Mazer Chemical Company, Chicago, IL.
Emulsion gel base component, 300.00 grams, was placed in a 2 liter
stainless steel beaker equipped with a Cowles Series 2000 mixer and heated
in a water bath to 80.degree. C. while adding the isostearic acid and
sorbitan monolaurate. Water at 90.degree. C. was then added slowly over a
10 minute period while mixing at 2500-3000 rpm. The mixture was mixed for
another five minutes, for a total of 15 minutes to form an emulsion. The
emulsion was allowed to cool to room temperature. After 24 hours a
supernant layer of fluid formed above the gel phase due to syneresis. The
emulsion did not separate into separate phases. The sample was designated
Example VI-A, Sample No. 15931-17-1.
An amount of a polyalkenyl polyether, Carbopol.RTM. 1622, 0.04 grams, 0.02
wt. % of the final emulsion was placed in a 600 ml stainless steel beaker
equipped with a Cowles mixer. A portion of the emulsion, 200.00 grams, was
added to the beaker and mixed at room temperature and low speed for 10
minutes. The product Example VI-B, Sample No. 15931-17-2 was allowed to
stand for a period of 24 hours. A supernatant layer of fluid appeared
above the gel phase due to syneresis. The emulsion did not separate into
separate phases.
An amount of a coating additive, 3M's Fluorad.RTM. additive FC-430, 0.04
grams, 0.02 wt. % of the final emulsion was placed in a 600 ml stainless
steel beaker equipped with a Cowles mixer. A portion of the emulsion,
200.00 grams was added to the beaker and mixed at room temperature and low
speed for 10 minutes. A 1/8 inch oil layer formed on top of the sample
within 30 minutes. After 24 hours, the emulsion composition, Example VI-C
had separated into three phases. The sample was No. 15931-17-3.
An additional 0.06 grams of polyalkenyl polyester, Carbopol.RTM. 1622, 0.03
wt. %, of the final emulsion was placed in a 600 ml stainless steel beaker
equipped with a Cowles mixer. Example VI-B, Sample No. 15931-17-2, 200
grams, was added to the beaker. The mixture was heated in a water bath to
50.degree. C. and mixed at low speed for 10 minutes. After 24 hours, a
supernatant layer of fluid had appeared above the gel phase of the sample
due to syneresis. The emulsion Example VI-D, Sample No. 15931-17-4, did
not separate into separate phases.
EXAMPLE VII
The procedure of Example IV was repeated with the following formulation:
______________________________________
Gel Parts % %
Component By Weight Grams Weight
Solids
______________________________________
Polybutene H-300
1.000 27.08 7.31 7.31
Al Stearate.sup.1
0.183 4.95 1.34 1.34
Triethylamine
0.085 2.30 0.62 0.62
Mineral Spirits
4.272 115.67 31.23
Gel Total 5.540 150.00 40.50
Emulsion Component
Refined Linseed Oil
0.100 2.71 0.73 0.73
Deionized Water
8.040 217.69 58.77
Total 13.680 370.40 100.00
10.02
______________________________________
Note:
.sup.1 No. 5503, Mallinckrodt Specialty Chemicals Co., St. Louis, Mo.
Gel component, 150.00 grams, was added to a 1.2 liter stainless steel
beaker. The refined linseed oil was added and the mixture heated to
70.degree.-80.degree. C. in a water bath. The beaker was then put under a
Cowles mixer. The deionized water was then added slowly over 8 minutes
while mixing at 200-300 rpm. Mixing was continued for 7 minutes. An oil
phase was visible, approximately of 0.5 inch, within 15 minutes. The
product was designated 15931-24 emulsion sample.
To 200.00 grams of the gel base, No. 15931-25, was added 0.02 wt %
polyalkenyl polyether Carbopol.RTM. 1622, 0.04 grams. The mixture was
mixed for 10 minutes at slow speed, less than 2000 rpm. An oil appeared
within 24 hours upon the surface of the gel due to syneresis. The emulsion
did not separate into separate phases. The sample was designated
15931-24-2.
To another 200.00 grams of sample 15931-24 there was added 0.04 grams
Fluorad.RTM. FC-129, approximately 230 ppm. The resulting mixture was
remixed for 5 minutes by hand, stirring with a stainless steel spatula. An
oily fluid separated from the gel within about 30 minutes, appearing on
the surface of the gel. This sample was 15931-24-3.
To 200 grams of sample 15931-24-2, there was added 0.04 grams, Fluorad.RTM.
FC-129, approximately 230 ppm. The sample was remixed for 5 minutes by
hand, stirring with a stainless steel spatula. An oily fluid separated
from the gel within about 30 minutes, appearing in the surface of the gel.
This sample was 15931-24-4.
EXAMPLE VIII
Polybutene emulsions were prepared according to the following formula:
______________________________________
Gel Parts %
Component By Weight Grams Weight
______________________________________
Polybutene H-300
1.000 27.08 7.31
Al Stearate.sup.1
0.183 4.95 1.34
Triethylamine
0.085 2.30 0.62
Mineral Spirits
4.272 115.66 31.24
Gel Total 5.540 149.98 40.51
Emulsion Component
Isostearic Acid
0.100 2.71 0.73
Deionized Water
8.040 217.69 58.76
Total 13.680 370.28 100.00
______________________________________
Note:
.sup.1 No. 5503, Mallinckrodt Specialty Chemicals Co., St. Louis, Mo.
After mixing according to the procedure of Example IV, an emulsion was
formed which separated in less than 10 minutes. To a portion of the
separated composition, 166.0 grams, there was added 0.083 grams, 0.05% wt.
%, Carbopol.RTM. 1622. The mixture was heated to 50.degree. C.
(122.degree. F.) and mixed for 10 minutes at 2000-3000 rpm. A stable
emulsion was formed, Sample No. 15735-143-3. The polybutene emulsion was
tested as a wood sealer against moisture absorption by a modified version
of ASTM D 3502-76.
Test specimens of cedar, one inch square by three inches long were
oven-dried for 24 hours at 50.degree. C. (122.degree. F.). A screw eye,
weight approximately 1 gram, was inserted into one end to form a specimen
assembly. Each specimen was weighed and stored in a desiccator over
calcium sulfate until being painted with a coating of the polybutene
emulsion.
Each wood block test specimen was coated with the polybutene emulsion on
all six sides with a brush, then hung on a drying rack in a hood for 24
hours to dry. Each test sample was prepared in duplicate.
Each test sample after drying was recoated once with the polybutene
emulsion and hung to dry again for 24 hours. Each test sample was then
weighed. A rod was inserted through the eye screw and each test sample was
placed in a 16 oz. glass container, the rod suspending the test sample in
the middle of the container. Weights were hung on the ends of each rod to
secure the rod's position. Water was slowly added to each container
without any water being poured directly on the test sample. The test
specimens floated in the water and tilted to one side. The water level was
raised until one top edge of the test sample was immersed in water but the
screw hole of the eye screw was dry to prevent water absorption into the
interior of the test sample by the screw hole. Tap water used had a
hardness of less than 300 grains. The test samples remained immersed in
water for 24 hours. Temperature was 22.degree. C. The test samples were
removed from the water, dried with absorbent paper and reweighed.
Percent weight gain was determined, [(final weight less coated weight)
divided by (dry weight plus coating weight less weight of the screweye)]
times 100. Sample number was 15735-143-3. Results are in Table II.
TABLE II
______________________________________
Water Absorption and Coating Conditions
Step Component Sample No. 15735-143-3
______________________________________
A. Block-Screw Eye Assembly
66 66A
B. Assembly Plus Coating
17.47 g 17.72 g
C. Weight of Coating 1.20 g 1.16 g
D. Coating Weight-% of Total
7.86% 7.46%
E. Weight After Immersion
19.72 g 20.11 g
F. Water Absorbed-Weight
2.25 g 2.39 g
G. Water Absorbed-% 13.66% 14.29%
H. Water Absorbed-% Average
13.98%
Condition of Coatings
I. After 24 hours Slight Tack Slight Tack
J. After 48 hours Slight Tack Slight Tack
______________________________________
EXAMPLE IX
The formulation and procedure of Example VI were used to prepare a series
of samples. The initial product No. 15931-17, was divided into four
batches, three of 200 grams each and one of 300 grams. The 300 gram batch,
No. 15931-17, was retained as a control. To one batch, No. 15931-17-4,
there was added, with low speed mixing for 10 minutes at 50.degree. C.,
0.10 grams of Carbopol.RTM. 1622 0.05% of total weight of the emulsion. In
the same procedure, 0.04 grams, 0.02 wt % of the emulsion, of FC-430 was
added to the emulsion, No. 15931-17-3. Each batch was divided into two
equal parts and tested by the procedure of Example VIII. A test specimen
of cedar, to which no coating was applied to the raw wood was also tested
as a blank to determine application response to each coating applied.
Results are in Table III.
TABLE III
______________________________________
Cedar Block Water Absorption
Blank-
No 15931-17-4
15931-17-3
Coat- 15931-17 Plus Plus
ing No Carbopol .RTM.
Carbopol .RTM.
FC-430
Step.sup.1
69 70 70A 71 71A 72 72A
______________________________________
A. 14.85 g 14.99 g 14.98 g
14.94 g
14.52 g
15.03 g
14.84 g
B. 15.70 g 16.40 g 16.33 g
16.28 g
15.90 g
16.61 g
16.46 g
C. 0.85 g 1.41 g 1.35 g
1.34 g
1.38 g
1.58 g
1.62 g
D. 6.13% 10.06% 9.63%
9.59% 10.18%
11.23%
11.68%
E. 23.76 g 19.58 g 19.92 g
19.99 g
19.52 g
18.82 g
18.43 g
F. 8.06 g 3.18 g 3.59 g
3.71 g
3.62 g
2.21 g
1.97 g
G. 54.76% 20.62% 23.36%
24.23%
23.23%
14.12%
12.72%
H. 54.76% 21.99 24.23% 13.42%
I No Sl. Tack Sl. Tack Some Tack
Tack
J. No Sl. Tack Some Tack Medium Tack
Tack
______________________________________
.sup.1 See Table II for step component designation.
The above data indicate that Carbopol.RTM. improves emulsion stability but
increases moisture absorption, whereas FC-430 decreases moisture
absorption but increases emulsion instability.
EXAMPLE X
In the procedure of Example IV, a sealer composition was prepared, the gel
formulation and emulsifier formulation were as follows:
______________________________________
Sample No. 15735-151-2
Gel Parts %
Component By Weight Grams Weight
______________________________________
Polybutene H-300
1.000 27.075 6.81
Al Stearate.sup.1
0.183 4.950 1.25
Triethylamine 0.085 2.300 0.58
Mineral Spirits
4.272 115.660 29.11
Gel Total 5.540 149.980 37.75
Emulsion Component
Ospstearoc Acid
0.150 4.06 1.02
Sorbitan Monolaurate
0.050 1.35 0.34
Deionized Water
8.940 241.94 60.89
Total 14.680 387.35 100.00
______________________________________
Note:
.sup.1 No. 5503, Mallinckrodt Specialty Chemicals Co., St. Louis, Mo.
Sample No. 15735-151-2 was divided into Sample Nos. 15735-151-3 and
15735-151-5. To No. 15735-151-2 there was added 0.2 wt %, Carbopol.RTM.
1622, and to No. 15735-151-5, there was added 0.2 wt % Carbopol.RTM. 934
plus 0.1 wt. % Carbopol.RTM. 1622, Cedar blocks were prepared as in
Example VIII and tested as 67 and 67A samples, and 68 and 68A samples.
Results are in Table IV.
TABLE IV
______________________________________
Cedar Block Water Absorption
Sample No.
157-151-3 15735-151-5
0.2% Wt. %
0.3 Wt %.sup.1
Carbopol .RTM.
1622 Carbopol .RTM.
Step Component 67 67A 68 68A
______________________________________
A. Block-Screw Eye 16.08 g 17.28 g
16.68 g
16.06 g
Assembly
B. Assembly Plus Coating
17.30 g 18.58 g
17.88 g
17.20 g
C. Weight of Coating
1.22 g 1.30 g
1.20 g
1.14 g
D. Coating Weight -% of
8.09% 7.99%
7.65%
7.57%
Total
E. Weight After Immersion
20.80 g 22.85 g
22.07 g
21.15 g
F. Water Absorbed-Weight
3.50 g 4.27 g
4.19 g
3.95 g
H. Water Absorbed-%
22.88% 24.60%
Average
Condition of Coatings
I After 24 hours Sl. Tack Sl. Tack
J. After 48 hours Sl. Tack Very Sl. Tack
______________________________________
Note:
.sup.1 0.1 wt. % Carbopol .RTM. 1622 plus 0.2 wt. % Carbopol .RTM. 934
EXAMPLE XI
The formulation of Example VII was tested for water absorption as in the
procedure of Example VIII. Samples of 200 grams were prepared as Samples
Nos. 15931-24-3 and 15931-24-4. No. 15931-24-3 contained 0.04 grams
Fluorad.RTM. FC-129 (approximately 230 ppm). No. 15931-24-4 contained 0.04
grams Fluorad.RTM. FC-129 plus 0.04 grams Carbopol.RTM. 1622 and tested as
samples 75 and 75A, and 76 and 76A. Details are in Table V.
TABLE V
______________________________________
Cedar Block Water Absorption
Sample No.
15931-24-3
15931-24-4
0.02 Wt. %
Carbopol .RTM.
0.02 Wt. %
1622 + 0.02 Wt.
Fluorad .RTM.
% Fluorad .RTM.
FC-129 FC-129
Step Component 75 75A 76 76A
______________________________________
A. Block-Screw Eye
14.84 g 14.85 g
15.36 g
15.43 g
Assembly
B. Assembly Plus Coat-
16.06 g 15.99 g
16.16 g
16.18 g
ing
C. Weight of Coating
1.22 g 1.14 g
0.80 g
0.75
D. Coating Weight-% of
8.80% 8.21%
5.56%
5.18%
Total
E. Weight After Immer-
18.34 g 18.58 g
19.30 g
18.88 g
sion
F. Water Absorbed-
2.28 g 2.59 g
3.14 g
2.70 g
Weight
G. Water Absorbed-%
15.12% 17.24%
20.67%
17.74%
H. Water Absorbed-%
16.18% 19.20%
Average
Condition of Coatings
I. After 24 hours Medium Tacky
Some Tacky
J. After 48 hours Very Tacky Medium Tacky
______________________________________
The above data indicate that although water absorption level is acceptable,
the tacky surface condition is unacceptable.
EXAMPLE XII
In the procedure of Example IV, a sealer composition was prepared. The gel
formulation and emulsifier formulation were as follows:
______________________________________
Sample No. 15931-26
Gel Parts %
Component By Weight Grams Weight
______________________________________
Polybutene H-300
1.000 27.08 6.38
Al Stearate.sup.1
0.183 4.95 1.17
Triethylamine
0.085 2.30 0.54
Mineral Spirits
4.272 115.67 27.25
Gel Total 5.540 150.00 35.34
Emulsifier Compound
Refined Linseed Oil
0.100 2.71 0.64
Isostearic Acid
0.150 4.06 0.96
Sorbitan Monolaurate
0.050 1.35 0.32
Deionized Water
9.840 266.43 62.76
Total 15.680 424.55 100.02
______________________________________
Note:
.sup.1 No. 5503, Mallinckrodt Specialty Chemicals Company., St. Louis, MO
Sample No. 15931-26 was divided into 200 gram samples Nos. 15931-26 and
159-26-2. Sample No. 15931-26 was tested as 77 and 77A. To Sample No.
15931-26-2, there was added 0.04 grams Carbopol.RTM. 1622, 0.02 wt. %,
Cedar blocks were prepared as in Example VIII and tested as 77 and 77A
samples and 78 and 78A samples. Results are in Table VI.
TABLE VI
______________________________________
Cedar Blocks Water Absorption
Sample No.
15931-26 15931-26-2
0.02 Wt. %
Carbopol .RTM.
1622
Step Component 77 77A 78 78A
______________________________________
A. Block-Screw Eye 14.54 g 15.17 g
14.68 g
15.26 g
Assembly
B. Assembly Plus Coating
15.71 g 16.45 g
15.59 g
16.15 g
C. Weight of Coating
1.17 g 1.28 g
0.91 g
0.89 g
D. Coating Weight-% of
8.62% 9.01%
6.63%
6.22%
Total
E. Weight After Immersion
18.70 g 19.01 g
20.50 g
20.81 g
F. Water Absorbed-Weight
2.99 g 2.56 g
4.91 g
4.66 g
G. Water Absorbed-%
20.28% 16.54%
33.56%
30.60%
H. Water Absorbed-%
18.41% 32.11%
Average
Condition of Coatings
I. After 24 hours Slight Tack Slight Tack
J. After 48 hours Some Tack Some Tack
______________________________________
The above data indicate that a sealer containing refined linseed oil,
isostearic acid and sorbitan monolaurate has an acceptable level of water
absorption but a level of tackiness remains which makes the formulation
unacceptable. The addition of Carbopol.RTM. 1622 also increased the water
absorbed.
EXAMPLE XIII
In the procedure of Example IV, a sealer composition was prepared. The gel
formulation and emulsifier formulation were as follows:
______________________________________
Sample No. 15931-82
Gel Parts %
Component By Weight Grams Weight
______________________________________
Polybutene H-300
1.000 15.27 2.46
Al Stearate.sup.2
0.400 6.11 0.98
Triethylamine
0.186 2.84 0.46
Turpentine 2.998 45.78 7.36
Gel Total 4.584 70.00 11.26
Emulsion Component
Isostearic Acid
0.150 2.29 0.37
Sorbitan Monolaurate
0.050 0.76 0.12
Adipic Acid Ester.sup.1
0.250 3.82 0.61
Deionized Water
35.686 544.94 87.64
Total 40.320 621.81 100.00
______________________________________
Note:
.sup.1 Smithol 50, Werner G. Smith, Inc., Cleveland, OH.
.sup.2 No. 5503, Mallinckrodt Specialty Chemicals Co., St. Louis, Mo.
The above emulsion, after 24 hours at room temperature, indicated no
separation. After 48 hours there was evidence of a mild separation of
phases which had not increased after 96 hours at room temperature.
Test specimens were prepared in the procedure of Example VIII to determine
water absorption and condition of the sealer coatings and tested as Sample
No. 15931-82. Results are in Table VII.
TABLE VII
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Cedar Block Water Absorption
Sample No. 15931-82
Step Component 108 108A
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A. Block-Screw Eye Assembly
15.30 g 14.93 g
B. Assembly Plus Coating
16.14 g 15.73 g
C Weight of Coating 0.84 g 0.80 g
D. Coating Weight-% of Total
5.87% 5.73%
E. Weight After Immersion
20.41 g 20.38 g
F. Water Absorbed-Weight
4.27 g 4.65 g
G. Water Absorbed-% 28.18% 31.50%
H. Water Absorbed-% Average
29.84%
Condition of Coatings
I. After 24 hours No Tack No Tack
J. After 48 hours No Tack No Tack
______________________________________
The above data indicate that an adipic acid ester of a linear alcohol
improves emulsion stability but increases moisture absorption.
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